CN117293422A - Method for inducing uniform deposition of zinc cathode of water-based zinc ion battery - Google Patents
Method for inducing uniform deposition of zinc cathode of water-based zinc ion battery Download PDFInfo
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- CN117293422A CN117293422A CN202311481043.1A CN202311481043A CN117293422A CN 117293422 A CN117293422 A CN 117293422A CN 202311481043 A CN202311481043 A CN 202311481043A CN 117293422 A CN117293422 A CN 117293422A
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- zinc
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- zinc ion
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011701 zinc Substances 0.000 title claims abstract description 65
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000008021 deposition Effects 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000001939 inductive effect Effects 0.000 title claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 88
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002738 chelating agent Substances 0.000 claims abstract description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 20
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 20
- 229960001763 zinc sulfate Drugs 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 14
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 10
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 10
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 10
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- -1 zinc tetrafluoroborate Chemical compound 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- 239000002000 Electrolyte additive Substances 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- 210000004027 cell Anatomy 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 17
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 13
- 239000006259 organic additive Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 210000001787 dendrite Anatomy 0.000 description 9
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for inducing uniform deposition of a zinc cathode of a water-based zinc ion battery, which is to add an electrolyte modification additive, such as an amino carboxylic acid chelating agent, capable of inducing uniform and compact deposition of the zinc cathode of the water-based zinc ion battery into the electrolyte of the water-based zinc ion battery. The electrolyte additive provided by the invention can improve the capacity retention rate of the water-based zinc ion battery to a certain extent, prolong the service life of the whole battery of the water-based zinc ion battery and obviously improve the electrochemical performance of the water-based zinc ion battery.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion batteries, and particularly relates to an electrolyte modification additive for inducing uniform deposition of a zinc cathode of a water-based zinc ion battery and an electrolyte containing the modification additive.
Background
As the demand for electric vehicles and portable electronic products has been increasing, rechargeable metal ion batteries have been rapidly developed. Lithium ion batteries have been the dominant energy storage market. However, the disadvantages of high price and uneven distribution of lithium resources, flammability and toxicity of organic electrolyte, etc. seriously hamper future development of lithium ion batteries. In recent years, water-based zinc ion batteries (AZBs) have low cost, environmental friendliness, abundant raw materials and high theoretical capacity (820 mAh g) -1 ) And the like, and is widely paid attention to. With conventional alkaline zinc metalUnlike cells, AZBs use weak acid solutions as electrolytes, with better reversibility and higher capacity retention. More than ten Zn salts have been reported as electrolytes for AZBs. Wherein ZnCl 2 、Zn(NO 3 ) 2 、Zn(ClO 4 ) 2 Due to the narrow anodic potential window (ZnCl) 2 ) Strong oxidizing property (Zn (NO) 3 ) 2 And Zn (ClO) 4 ) 2 ) Are not suitable as electrolytes for high performance AZBs. In contrast, zn (CF) 3 SO 3 ) 2 And Zn (TFSI) 2 The electrolyte can promote Zn 2+ Migration kinetics and stability of Zn anode are improved, and the Zn anode has obvious electrochemical performance. However, the high cost of these electrolytes would limit their large-scale use in commercial AZBs. Whereas ZnSO 4 The electrolyte has the advantages of low cost, good stability, good performance on most cathodes and the like, and is widely applied to AZBs.
Although based on ZnSO 4 The AZBs of the electrolyte have outstanding advantages and application prospects, but the zinc anode of the zinc ion battery still faces zinc dendrite growth problems, corrosion problems, hydrogen evolution reaction passivation problems, dead zinc problems and the like. Notably, the above-mentioned problems are not independent, and the formation of dendrites on the surface of the zinc electrode leads to acceleration of the electrolyte hydrogen evolution reaction, and local pH changes lead to OH - Increase with SO in solution 4 2- 、H 2 O and the like generate insoluble byproducts, so that the surface of the zinc cathode is uneven, the polarization is increased, and the formation of zinc dendrites is accelerated in turn. This vicious circle continues to damage the zinc anode, resulting in a decrease in electrode coulomb efficiency and thus in cell failure. Therefore, the reversible deposition and stripping of the zinc cathode can be obviously improved by the measures which can regulate and control the independent steps.
Wherein, the inhibition of zinc dendrite growth mainly starts from the two aspects of zinc cathode self design and electrolyte optimization. The design of the zinc cathode mainly comprises the surface modification of the zinc cathode and the design of a three-dimensional structure current collector, but both measures require a great deal of time cost and process cost. The process of zinc deposition is closely related to the electrolyte, which is one of the key factors affecting zinc dendrites. The optimized electrolyte has remarkable effect in inhibiting zinc dendrite growth, and meanwhile, a trace amount of additive does not need to be put into too much process cost, so that the electrolyte is one of important means for maintaining the structural stability of the battery and prolonging the cycle life.
Researchers find that the low self-diffusion barrier along the (002) plane promotes the two-dimensional diffusion and horizontal galvanization of metallic zinc, can effectively avoid the generation of zinc dendrites, improves the cycle stability of the battery, for example, cyclodextrin is added as an electrolyte additive in the prior art, but is used as an organic macromolecule, and is difficult to enter a solvation structure of zinc ions so as to achieve the dual effects of solvation regulation and interface adsorption, and is difficult to realize high-current and high-capacity charge and discharge test.
Disclosure of Invention
The invention mainly provides an additive for an electrolyte of a water-based zinc ion battery, and aims to solve the problems of short circuit, side reaction, corrosion and the like of the battery caused by common dendrite growth in the water-based zinc ion battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention firstly provides a method for inducing uniform deposition of a zinc cathode of a water-based zinc ion battery, which is characterized in that an electrolyte modifying additive capable of inducing uniform and compact deposition of the zinc cathode of the water-based zinc ion battery is added into the electrolyte of the water-based zinc ion battery.
Further, the electrolyte modifying additive is an aminocarboxylic acid chelating agent such as diethyl triamine penta acid, sodium nitrilotriacetate, ethylenediamine tetraacetic acid and the like. By using the additive to induce the zinc ions in the water-based zinc ion battery to be uniformly deposited in the process of dissolution/deposition in an orientation (002) crystal face, the uniform and flat zinc cathode surface is realized in the process, and the aim of optimizing the performance of the water-based zinc ion battery is fulfilled.
Further, the addition amount of the electrolyte modifying additive in the electrolyte is 0.005-0.5mol/L.
The invention also discloses a water-based zinc ion battery electrolyte, which comprises the components of a solvent, an electrolyte and the electrolyte modification additive.
Further, the solvent is deionized water.
Further, the electrolyte is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate dihydrate, zinc perchlorate, zinc tetrafluoroborate and zinc trifluoromethane sulfonate, and the concentration of the electrolyte in the electrolyte is 0.1-10mol/L.
The invention further provides an aqueous zinc ion battery, wherein the electrolyte is the electrolyte containing the aminocarboxylic acid chelating agent as an additive.
Further, the negative electrode of the water-based zinc ion battery is made of metallic zinc, the positive electrode material is one of vanadium-based compounds, manganese-based compounds, prussian blue analog polyanion compounds and organic matters, and the diaphragm is a glass fiber microporous membrane.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the electrolyte additive such as diethyl triamine penta acid is adsorbed on the surface of the zinc cathode, and a SEI layer is formed in situ, so that the ionic conductivity can be improved, the solvation structure of zinc ions can be regulated and controlled, the electrolyte additive is anchored on the surface of the zinc cathode and the preferred orientation of zinc (002) is induced, and the purpose of stabilizing the zinc cathode is realized.
2. The electrolyte additive provided by the invention can greatly improve the stability of the zinc ion battery, such as the zinc ion battery in 5mAcm -2 The stability to zinc of the additive is up to more than 1800 hours under the condition of high current density, and the stability to zinc is obviously improved compared with common electrolyte. At the same time at 30mAcm -2 Can still circulate for more than 80 hours under the ultra-high current density.
3. The electrolyte additive provided by the invention can improve the capacity retention rate of the water-based zinc ion battery to a certain extent, prolong the service life of the whole battery of the water-based zinc ion battery and obviously improve the electrochemical performance of the water-based zinc ion battery.
4. The electrolyte provided by the invention has the inherent advantages of safety, environmental protection, simple preparation method, wide application range and the like, can obviously inhibit the generation of byproducts, optimize the performance of the water-based zinc ion battery, improve the cycling stability and the battery life of the water-based zinc ion battery, and has a great application prospect and research value in the fields of zinc ion batteries and other potential new energy batteries.
Drawings
FIG. 1 shows the result of experiment 1 at 5mAcm -2 Current density of 5mAh cm -2 Comparative plot of zinc stability for zinc-zinc symmetric cells assembled from the electrolyte of example 3 and comparative example 1.
FIG. 2 shows the measurement of 30mAcm in Experimental example 1 -2 Is 30mAh cm -2 Comparative plot of zinc stability for zinc-zinc symmetric cells assembled from the electrolyte of example 3 and comparative example 1.
Fig. 3 is a graph showing comparison of coulombic efficiency of zinc-copper asymmetric cells assembled from the electrolytes of example 3 and comparative example 1 in experimental example 2.
FIG. 4 shows a zinc-zinc symmetrical cell assembled from the electrolytes of example 3 and comparative example 1 in experimental example 3 at 5mA cm -2 XRD contrast pattern after 100h of cycling at current density.
FIG. 5 shows a zinc-zinc symmetrical cell assembled from the electrolytes of example 3 and comparative example 1 in experimental example 4 at 5mA cm -2 SEM comparison after 50h of cycle at current density of (c) and (d) of comparative example 1, and (a) and (b) of comparative example 1, respectively, and (c) and (d) of example 3.
FIG. 6 shows a zinc-zinc symmetrical cell assembled from the electrolyte of example 3 of Experimental example 5 at 10mAcm -2 XRD patterns after various times of deposition at current densities of (c).
FIG. 7 shows a zinc-zinc symmetric cell assembled from the electrolyte of comparative example 1 of Experimental example 5 at 10mAcm -2 XRD patterns after various times of deposition at current densities of (c).
FIG. 8 shows the Zn// V composition of the electrolytes of example 3 and comparative example 1 in Experimental example 6 2 O 5 The cycle performance of a full cell at a current density of 2A/g is compared.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc acetate dihydrate and diethyl triamine penta acid, wherein the concentration of the zinc acetate dihydrate is 2mol/L, and the concentration of the diethyl triamine penta acid is 20mmol/L.
Example 2
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc trifluoromethane sulfonate and diethyl triamine penta acid, wherein the concentration of the zinc trifluoromethane sulfonate is 2mol/L, and the concentration of the diethyl triamine penta acid is 20mmol/L.
Example 3
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc sulfate and diethyl triamine penta acid, wherein the concentration of the zinc sulfate is 2mol/L, and the concentration of the diethyl triamine penta acid is 20mmol/L.
Example 4
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc sulfate and diethyl triamine penta acid, wherein the concentration of the zinc sulfate is 2mol/L, and the concentration of the diethyl triamine penta acid is 50mmol/L.
Example 5
The electrolyte containing the organic additive for the aqueous zinc ion battery of the present example was a mixed aqueous solution of zinc acetate dihydrate and sodium nitrilotriacetate, wherein the concentration of zinc acetate dihydrate was 2mol/L and the concentration of sodium nitrilotriacetate was 20mmol/L.
Example 6
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc trifluoromethane sulfonate and sodium nitrilotriacetate, wherein the concentration of the zinc trifluoromethane sulfonate is 2mol/L, and the concentration of the sodium nitrilotriacetate is 20mmol/L.
Example 7
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc sulfate and sodium nitrilotriacetate, wherein the concentration of the zinc sulfate is 2mol/L, and the concentration of the sodium nitrilotriacetate is 20mmol/L.
Example 8
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc trifluoromethane sulfonate and ethylenediamine tetraacetic acid, wherein the concentration of the zinc trifluoromethane sulfonate is 2mol/L, and the concentration of the ethylenediamine tetraacetic acid is 20mmol/L.
Example 9
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc acetate dihydrate and ethylenediamine tetraacetic acid, wherein the concentration of the zinc acetate dihydrate is 2mol/L, and the concentration of the ethylenediamine tetraacetic acid is 20mmol/L.
Example 10
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc sulfate and ethylenediamine tetraacetic acid, wherein the concentration of the zinc sulfate is 2mol/L, and the concentration of the ethylenediamine tetraacetic acid is 20mmol/L.
Example 11
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc sulfate, manganese sulfate and diethyl triamine penta acid, wherein the concentration of the zinc sulfate is 2mol/L, the concentration of the manganese sulfate is 0.1mol/L, and the concentration of the diethyl triamine penta acid is 20mmol/L.
Example 12
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc sulfate, manganese sulfate and sodium nitrilotriacetate, wherein the concentration of the zinc sulfate is 2mol/L, the concentration of the manganese sulfate is 0.1mol/L, and the concentration of the sodium nitrilotriacetate is 20mmol/L.
Example 13
The electrolyte containing the organic additive for the aqueous zinc ion battery of the embodiment is a mixed aqueous solution of zinc sulfate, manganese sulfate and ethylenediamine tetraacetic acid, wherein the concentration of the zinc sulfate is 2mol/L, the concentration of the manganese sulfate is 0.1mol/L, and the concentration of the ethylenediamine tetraacetic acid is 20mmol/L.
Comparative example 1
The electrolyte for the aqueous zinc ion battery of the comparative example was a zinc sulfate aqueous solution in which the concentration of zinc sulfate was 2mol/L.
Comparative example 2
The electrolyte for the aqueous zinc ion battery of the comparative example is a zinc trifluoromethane sulfonate aqueous solution, wherein the concentration of the zinc trifluoromethane sulfonate is 2mol/L.
Comparative example 3
The electrolyte for the aqueous zinc ion battery of the comparative example was a zinc acetate dihydrate aqueous solution in which the concentration of zinc acetate dihydrate was 2mol/L.
Comparative example 4
The electrolyte for the aqueous zinc ion battery of this example was a mixed aqueous solution of zinc sulfate and manganese sulfate, wherein the concentration of zinc sulfate was 2mol/L and the concentration of manganese sulfate was 0.1mol/L.
Experimental example 1
A zinc-zinc symmetrical battery was prepared using different electrolytes (electrolytes configured in example 3 and comparative example 1). And respectively taking zinc foil as positive and negative electrode pieces of the button cell. Firstly, placing a positive electrode plate into a positive electrode shell, then placing a glass fiber diaphragm, then dripping 0.15mL of prepared electrolyte, then placing a negative electrode plate above the glass fiber diaphragm, then sequentially placing a gasket and an elastic sheet, finally buckling the negative electrode shell, and packaging a battery by a battery packaging machine to obtain the required zinc-zinc symmetrical battery. Then constant-current charge and discharge test is carried out on the prepared zinc-zinc symmetrical battery, wherein the current density for the test is 5mA cm -2 The test results are shown in FIG. 1. Even at 30mA cm -2 Is greater than 30mAh cm -2 Can also be circulated for more than 80 hours under the condition of super-large capacity, as shown in figure 2. From the results of the tests conducted in the examples and comparative examples, it can be seen that the addition of diethylenetriamine pentaacetic acid greatly prolongs the cycle life of the zinc-zinc symmetrical cell.
Experimental example 2
And manufacturing the zinc-copper asymmetric battery. The copper foil is used as a positive pole piece of the button cell, and the zinc foil is used as a negative pole piece of the button cell. Firstly, placing a positive electrode plate into a positive electrode shell, then placing a glass fiber diaphragm, then dripping 0.15mL of prepared electrolyte, then placing a negative electrode plate above the diaphragm, then sequentially placing a gasket and an elastic sheet, finally buckling the negative electrode shell, and packaging a battery by a battery packaging machine to obtain the water-based zinc ion asymmetric button battery. The electrolytes used therein were the electrolytes prepared in example 3 and comparative example 1, respectively. The purpose of the zinc-copper asymmetric cell was to test the coulombic efficiency of the cell, which is the ratio of the zinc stripping capacity to the deposition capacity on a zinc-free substrate, with larger values indicating better reversibility of zinc deposition/stripping. The test results are shown in fig. 3, and the addition of the additive obviously improves the coulombic efficiency of the battery, and the comparison analysis does not hardly result in that the addition of the electrolyte additive improves the reversibility of the deposition and stripping behaviors of the zinc cathode.
Experimental example 3
The zinc-zinc symmetrical cell prepared when using different electrolytes (electrolytes configured in example 3 and comparative example 1) was measured at 5mA cm -2 After 100 hours of cycling at the current density of (2) the cell was disassembled and the zinc sheet was subjected to X-ray diffraction test, the test results are shown in figure 4. From a comparison of the two, the zinc sheet can expose more (002) crystal faces after the additive is used, and a great deal of literature proves that the (002) crystal face exposure is more beneficial to uniform deposition of the zinc ion battery, so that the cycle performance of the zinc ion battery is promoted.
Experimental example 4
The zinc-zinc symmetrical cell prepared when using different electrolytes (electrolytes configured in example 3 and comparative example 1) was measured at 5mA cm -2 After 50 hours of circulation under the current density, the battery was disassembled, and the zinc plate was subjected to scanning electron microscopy, and the result of the scanning is shown in fig. 5. As can be seen by comparing the two, the surface of the zinc sheet using the electrolyte additive is smoother and flatter, while the surface of the zinc sheet without the additive is very uneven. The smooth and flat surface of the zinc anode is beneficial to inhibiting the generation of byproducts and reducing the rapid growth of zinc dendrites, so that the service life of the water-based zinc ion battery is greatly prolonged.
Experimental example 5
When different electrolytes (the electrolytes configured in example 3 and comparative example 1) were used for preparationThe zinc-zinc symmetrical cell of (C) is at 10mA cm -2 Is deposited continuously at a high current density, and the zinc sheet is subjected to an X-ray diffraction test after the battery is disassembled, and the test results are shown in fig. 6 and 7. As can be seen from comparison of the two, the surface of the zinc sheet after the additive is used gradually exposes more (002) crystal faces, which is consistent with experimental example 4, and further verification that the introduction of the additive promotes the deposition of the (002) crystal faces, thereby being beneficial to prolonging the cycle life of the zinc ion battery.
Experimental example 6
Preparation of Zn// V 2 O 5 The full battery is prepared by the following steps: preparation of positive plate: will V 2 O 5 Mixing conductive carbon black and polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1, taking N-methyl pyrrolidone (NMP) as a solvent, stirring for eight hours, uniformly coating the mixture on a titanium foil, and then drying the mixture at 80 ℃ for 12 hours to obtain the pole piece. (2) assembling an aqueous zinc ion battery: the aqueous zinc ion battery consists of the positive plate prepared in the step (1), the target electrolyte prepared in the example 3 and the comparative example 1, a diaphragm and a zinc negative electrode, wherein the diaphragm is made of glass fiber, the negative electrode is made of a metal zinc plate, and the assembly of the battery is completed in an atmosphere. FIG. 8 is a graph of the cycling performance of full cells prepared using different electrolytes, with a current density of 2A/g tested. The results show that the addition of electrolyte additives optimizes the capacity retention of the full cell to some extent.
Experimental example 7
Preparation of Zn// MnO 2 The full battery is prepared by the following steps: preparation of positive plate: mnO is added to 2 Mixing conductive carbon black and polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1, taking N-methyl pyrrolidone (NMP) as a solvent, stirring for eight hours, uniformly coating the mixture on a copper foil, and then drying the mixture at 80 ℃ for 12 hours to obtain the pole piece. (2) assembling an aqueous zinc ion battery: the aqueous zinc ion battery consists of the positive plate prepared in the step (1), the target electrolyte prepared in the example 11 and the comparative example 1, a diaphragm and a zinc negative electrode, wherein the diaphragm is made of glass fiber, the negative electrode is made of a metal zinc plate, and the assembly of the battery is completed in an atmosphere.
Claims (10)
1. A method for inducing uniform deposition of a zinc cathode of a water-based zinc ion battery is characterized in that an electrolyte modifying additive capable of inducing uniform and compact deposition of the zinc cathode of the water-based zinc ion battery is added into an electrolyte of the water-based zinc ion battery.
2. The method according to claim 1, characterized in that: the electrolyte modifying additive is an amino carboxylic acid chelating agent.
3. The method according to claim 1 or 2, characterized in that: the addition amount of the electrolyte modifying additive in the electrolyte is 0.005-0.5mol/L.
4. The method according to claim 2, characterized in that: the amino carboxylic acid chelating agent is at least one of diethyl triamine penta acid, sodium nitrilotriacetate and ethylenediamine tetraacetic acid.
5. An aqueous zinc-ion battery electrolyte containing an electrolyte modifying additive obtainable by a process according to any one of claims 1 to 4.
6. The aqueous zinc-ion battery electrolyte according to claim 5, further comprising a solvent and an electrolyte.
7. The aqueous zinc-ion battery electrolyte according to claim 6, wherein: the solvent is deionized water.
8. The aqueous zinc-ion battery electrolyte according to claim 6, wherein: the electrolyte is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate dihydrate, zinc perchlorate, zinc tetrafluoroborate and zinc trifluoromethane sulfonate.
9. The aqueous zinc-ion battery electrolyte according to claim 6 or 8, characterized in that: the concentration of the electrolyte in the electrolyte is 0.1-10mol/L.
10. An aqueous zinc ion battery comprising the electrolyte according to any one of claims 5 to 9.
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| CN115275399A (en) * | 2022-08-30 | 2022-11-01 | 北京理工大学长三角研究院(嘉兴) | Electrolyte solution and aqueous zinc ion battery using same |
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| CN115275399A (en) * | 2022-08-30 | 2022-11-01 | 北京理工大学长三角研究院(嘉兴) | Electrolyte solution and aqueous zinc ion battery using same |
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